Dimethyl Carbonate → Methyl 2-hydroxy-5,5-dimethylcyclohex-1-enecarboxylate

HRID 521398Notes

Reaction equation

HRID 521398 reaction equation
[C:1](=[O:6])([O:4][CH3:5])OC.[H-].[Na+].[CH3:9][C:10]1([CH3:17])[CH2:15][CH2:14][C:13](=[O:16])[CH2:12][CH2:11]1.C([O-])(O)=O.[Na+]>C1COCC1>[OH:16][C:13]1[CH2:14][CH2:15][C:10]([CH3:17])([CH3:9])[CH2:11][C:12]=1[C:1]([O:4][CH3:5])=[O:6]

Participants

6

Reactant 4

HCID 12021Dimethyl CarbonateHCID 24758Sodium hydrideHCID 138166Cyclohexanone, 4,4-dimethyl-HCID 516892Sodium Bicarbonate

Product 1

HCID 54676124Methyl 2-hydroxy-5,5-dimethylcyclohex-1-enecarboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of dimethyl carbonate (31.5 g, 350 mmol) in dry THF (600 mL) was added sodium hydride (14.4 g, 360 mmol) by portion at 0° C. The resulting mixture was stirred at 0° C. for 30 min and then was added a solution of 4,4-dimethylcyclohexanone (15 g, 119 mmol) in THF (150 mL) dropwise over 30 min. The resultant mixture was heated at 60° C.-80° C. for 3 h before cooled to room temperature. The reaction mixture was poured into saturated NaHCO3 solution and extracted with a mixture of 33% ethyl acetate in petroleum ether. The organic layer was washed with water, brine, dried over Na2SO4 and concentrated to give 26.5 g crude of methyl 2-hydroxy-5,5-dimethylcyclohex-1-enecarboxylate, which was used in next step without further purification. 1H NMR (DMSO-d6) δ 12.09 (s, 1H), 3.71 (s, 3H), 2.25-2.26 (m, 2H), 1.99 (s, 2H), 1.40-1.41 (m, 2H), 0.92 (s, 1H).

Workup

  1. temperaturebefore cooled to room temperature
  2. extractionextracted with a mixture of 33% ethyl acetate in petroleum ether
  3. washThe organic layer was washed with water, brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-1918f798a9424dcbbb30b50407f96f6e
Source dataset
uspto-grants-2016_05
Patent number
US09328111B2

Reaction notes

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